Coating composition and process of making it



. h Patented No vs Frank 1;. Root, Montclair, iv. 1., sssisnos to Ellis-'- Foster Company, a corporation of New Jracy i No Drawing. Applicationdanuary 21, 1-942,

Serial N0. 427,593

, s Claims. (01. etc-'29) This invention relates to fast-drying coating compositions and to the method of making them. g In particular it relates to air-drying coating which'dry so rapidly that a large .0!

coats can be applied in aday, if'desired. It is compositions which dry to an insoluble film permitting recoating'ln the same way as aponventional drying oil arnish but which are free from d y n oils, v Y

A conventional varnish consists of drying oil,

-,resin,' drier and-thinner. Resinand drying oil 'are heated together to form a plastic mas and a liquid coating composition is formed by dissolving thisin a volatile solvent or thinner and adding a drier. When the solution is'applied to a surface the thinner evap :rates leaving a sticky of oil and resin. Subsequent oxidation of r the oil produces a hard film which is no longer soluble in the solvents used in the original liquid composition. An oil varnish contains about 50 per. cent film-forming materials and 50 per cent volatile thinners, which are lost. The thickness of the dried film is; therefore, about half the thickness of the wet film as applied, so that,

also an object to prepare coating compositions which contain a relatively high content of 'filmforming material so that a dried finish of practical thickness is obtained by using a less number of coats than with a drying oil varnish. It is a further object to prepare coating compositions which in film form'dry on the interior and 'on the surface simultaneously. rather than first on' the surface as is the case with those varnishes .which depend on air-oxidation for hardening, thus' allowing the ,mater'ial'to be appliedin thick layers. Still another object is to provide a varnish for wood which permits rubbing and polish .ing' ina iminimuin of time or to provide fioor varnishesfiwood fillers and undercoats for conventional finishes. Other objects will be appar- 'ent irom the following:

Furfuryl alcoholis a. colorless, relatively highboiling liquid .(13. P. 171 C.) which resinifies two or more coats are necessary to get. the desired thickness 0 "time between coats and often a light sanding must be provided. Although present-da var-' nishes dry much faster: than older types, it'r emains that relativelylong time ,is required in finish. A1s0 suitable drying 'finishingjwith oil varnishesfor the reason that a dry n is largely a surface action which requires adequate time. Also, the film must not bethick. Lacquers dry so much fasten-than varnishes that they are widely used in preference. 7

A lacquer consists ofa solid film-forming mater-ial (nitrocellulose, shellac, etc.) dissolved in a volatile solvent. When a lacquer is applied to when in contact with acids." The-'resiniflcation reaction is highly exothermic and may proceed with almost explosive violence. The resin which is formed is insoluble, infusible anddark "c01- ored, (from deep yellow to black depending upon the amount of acid and the violence of the re- 1 Furfuryi alcohol can be resinified in 'actionis I the -iorm of a film by adding acid Just before the film is applied, but the dried film is dark -colored and the action'of the acid continues afterthe film is dry so that shrinkage and increasing-brittleness cause checkingor cracking. Also,-.th e mixture must be applied promptly, otherwise the alcohol becomes too viscousor i resinifies before it can be used. (Esters of fur- .a surface the solvent evaporates leaving the solid film-forming material as .a hard film. Drying L is faster than withvamishes since hardening 're--.

sults from the mere evaporation of the; solvent. However, a dried lacquer film is ,solublesin the originalsolventsused in preparing it, so that a lacquer can not readily-be applied with abrush to undercoats. A clear lacquer of suitable spraying consistency may contain 10 to 20 per cent solids and so to 90 'per cent of volatile relatively expensive solvents which are lost. The thickness r thejfinal dried film is aboutafifth that of the freshly applied film so that, in order to" build up a finish of practicaljthicknessm large number of coats is necessary. A thick of lacquer can not be applied because of .the necessity for solvent to escape readily.

It is an object of the present invention to furyl alcohol in general behave as does the alcohol itself. his a further object of this invention to prepare coating compositions from liquid derivatives of furfuryl alcohol which are stable fora relatively'longtime before use and which dry very rapidly to light-colored, durable films. This object is brought aboutby the preparation of a liquid resin base comprising a furfuryl alcohol-modified urea-formaldehyde 0011-.

densati on' product,'and addition thereto of data-- bilizer, a drying ac'celeratorand aplasticizer.

,The liquid'resin base is prepared by heating a mixture of urea, aqueous formaldehyde and furfuryl alcohol (forexample, a mixture consist ing of 1 mole of ureapfrom 2 to 4 moles-of formprovide coating compositions of. the varnish type to aldehyde and substantially 1- mole of furiuryl alcohol) to form a condensation product. 'I'hiourea may be-used in place of urea and formal- .dehyde polymers insteadof the aqueous aldehyde.

Improved water resistance is imparted to the dried film by replacing part-of the urea (say 5 to 25%) by an equivalent amount of a phenol. The condensation is preferably carried out in the presence of a very small amount of acid, such as that normally presentin aqueous formaldehyde, although initial formationof a methcontrolled so that drying to a recoatable stage ylol urea may be done in neutral or slightly alk'a- I line solution followed by condensation with furfuryl alcohol under slightly acid'conditions. Water is removed by distillation (preferably under reduced pressure) and the reaction product is obtained as a viscous liquid. If the condensation mixture is too acid during reaction some insoluble methylene urea may form and thi is removed by filtration before dehydration. Y

The liquid resin base dries very quickly when a small amount of acid is added. However, the film is. discolored and the acidified solution gels very quickly. Addition of various solvents re-i tards gelation of the acidified resin base somewhat. However, as will be shown later. tests with a large number of solvents indicate that there are only a few which both retard gelation,

of an acidified solution for an exceedingly longtime and also yield films which are light'colored. The amount of stabilizing solvent is not critical and need not exceed 20 per cent of the entire composition. Thus a coating composition is ob tainable which contains upwards of 80% of filmforming materials.

This coating composition is very fast drying (for example, it may be made to air-dry in less than an hour) so that several coats 'may be applied during a day. Also, afirst coat need not be thoroughly hard before a succeeding coat is applied. However, the fully dried coating is extremely hard so that checking is liable to occur relatively soon. Thus, a finish on wood made up of several coats of the resin base may show occurs in less than about an hour.

evaporation or dissociation from the composition. If too much acid is present the film dries with a yellow coloration and checks at an early date due to continuing action of the acid. With sulfuric acid the amount which produces suitable drying without yellowing and early checking is from about 0.3 to 0.7% of the composition. The same applies to such acids as sulfamic and toluenesulfonic. acids may be used in slightly greater amount. In general, the acid to be used is a strong one and has a degree of dissociation greater than 1x101 Peroxides (e. g., benzoyl peroxide) used along with an acid produce more rapid drying than an acid alone. I Since the proportion of acid which is used is small, acids are conveniently added as a solution in the-stabilizing solvent. I

The complete coating composition therefore comprises:

\ Parts Liquid resin base 100 Plasticizer .Q. 10-40 Stabilizing solvent 10-25 polymerizes, the color ranging from deep yellow) Hence,

checking in a month or so, particularly if an unduly large amount of acid is used. Additionof certain plasticizers controls checking so that durable finishesare possible. v

Plasticizers include the following terials:

types of ma- (a) glycerol sulfide (a viscous light-- colored substance obtained, for example, by re-- action of glycerol dichlorhydrin with sodium monosulfide) and reaction products of glycerol sulfide with formaldehyde and urea, thioulea or melamine; (b) unmodified 5 alkyd resins, particularly those prepared from dihydric alcohols and dicarboxylic acids, for example, esters of maleic, iumaric, succinic' and phthalic. acids;

and (c) glycerolsulfide-modified alkyd resins.

It may be remarked that the oil-modified alkyd resins which are'so useful in plasticizing ordie nary alcohol-modified urea resins (e. g., butanolmodified urea-formaldehyde) are not usable with the products of the present invention. They are miscible-in solution but yield cloudy films due to noncompatibility. The amount of plasticizer varies from about 10% to about 40% of the liquid resin base, depending mainly upon the use of the coating. Excessive amounts of plasticizer retard hardening of the film. Another type of plasticized (co-reaction) product is obtained by forming the furfuryl alcoholmodified urea-formaldehyde condensation product' in the presence of the plasticizer.

Resins of generally alcohol-soluble type such as shellac, accroides or the gasoline insoluble residue obtained by extracting pine, stumps (e. g., the resin sold as Vinsol) may be added to the compositions.

Drying accelerator 0.3-0.7 Pigments are incorporated to form enamels.

Appropriate fillers and extenders are used to prepare sealers or pore fillers and undercoats.

It is a characteristic property of furfuryl al-. cohol that it yields a dark-colored resin when it to black depending upon the conditions. it is surprising that the products of the present invention dry to light-colored films. remarked that phenol-formaldehyde resins prepared in the presence of furfuryl alcohol yield dried films of very dark color. In one case,

phenol and formaldehyde were reacted in fur-.

i'uryl alcohol under alkaline conditions to yield a clear light-colored solution. When acidified and applied as a coating the film dried to a dark green color. The same was true of p-amylphenol. As mentioned above, improved water resistance of the products of this invention is ,obtained when a portion of the urea is replaced by a phenol. When as much as 25 per cent of the urea is replaced by a phenol such as amylphenol to yield a phenol-modified condensation product of furfuryl alcohol, urea and formaldehyde the acidified product dries to a light color. The attainment of light-colored dried films from compositions containing phenols is a novel feature of this invention. Phenols suitable for use herein include phenol, cresols, xylenols, phenylphenol and alkylated phenols.

The following examples are illustrative of the products of this invention. They are not to be construed as limiting since many variations in product and process are possible.

' Example 1 This mixture was heated to boiling under reflux for 2 /2 hours. During this time a small amount of white insoluble matter (methylene urea) pre- Oxalic, phosphoric and maleic It may be Grams remove water. --"Ihe-product was a' clear, someaa a off a eip'it'ated. This was gilltered ofliand the'bl'eari I resetting canbedone. "Dry means that the solution concentrated under reducedpressure to 9 film is hard andilrm enouah'not to print when pressedwith the finger; A yellow' c'olor of dried I what viscous liquid. ,Addition er 5% ofxa 20%" I solution oi. sulfuric acidin ethyl'alcohol produced .a clear solution" which when spread asfa;

dried to ayellow hard film in#35"min'utes.' The solution-to which the acidwasadded rapidly J iilm is substantially the same degree oi'discolora- Working time is the time during which the & tion as shown by a /phenplic resin varnish (tor example, xylenol-i'ormaldehyde ,and tung oil).

composition may/ bekpt at-room temperature darkened and became warm. In about 10. min- I "(20 C.) and remain usable without further thinutes ithad' formed a hard insoluble gel. when 10 ninx.- fGel time is when the composition 'no' 20% of ethanol was added alongwith the acid- {longer flows. 1;

solution, a film dried in about the same'time and? It is evident that stabilizers for the varnish was light colored. Also, the acidified solution, --base comprisethose aliphatic monohydric alcothinned with 20% of alcohol remained of ,sub-

of less than 5 carbon atoms be remarked that amyl alcohol andpther aliphatic monohydric alcohols of more than 5'car-f bon atoms, butyl acetate, ethyl silicate, ethyl 25 ether, isopropyl ether, methyl isobutyl ketone and hydrocarbons of various types are not solvents I 3 for the liquid resin base. However, such liquids $2 2; may be used in mixture with a low boiling alco- 3rd :2 ,hol and may bedesirable for blending other ma- 9 4th :3 "f*-' terials such as resinsrand plasticizers with thev 5th wat l b* l 4:30.?

,stantiallrthe same viscosity o'r brushing condi- 16 r tion for about 5 hours with little change oicolon' KExample 2 In order to defln'e those solvents which,,.when Q added in relatively small amount, stabilize the v coating formed by mixing liquid'resin base toyield a composition having 1 Paris a lengthened workingtime and which co'mposi- 1Z0 h resin s 01 1 F 5 51 tionproduces last-drying light-colored films, elycemlmonvsulfidanf 9 a large number of liquids were tested.- It may Denatured q '1 A 20% solution of HrSOrin alcohol 2.

A clear solution of brushing consistency was formed. Five coats were applied (on the same day) toa wooden panel in the following sequence varnish base. The table shows the behavior or various solvents. e

i The following'daythei lhish was rubbed and pol- Film I l l Working i I Film Color 0! dried t Appearance-oi gel 93" L 5; dry illm' fi flf 9 24 hours) Minutes Minutes i Minutes Minutes l 1; -22 F :23 as 1? a Ethanol'(l00%).. 11 35- m aoo e00 01$! its soft 4 Isoprop'anol... 19 52 n 240 300' ar, soft 5 Ally] alcohol 26 77' n 300 600 'Do. 6 But ol..-.-l- 61 100.-.-.110 240 300 Do. 7 Sec. butyl alcohol.. 26 58 do 180 750 Do. 8 Ten-.but laleohoL. -23' 68 --l--do 90 400 Do,

9 -Benzyl eohoL- 42 9 Yellow 27. 100 Clear, hard 10 Diacetone alcohol 26 v 56 .....do l5 25 Do. 11 Cyclohexanol.. 31 60 do 70 00 Turbld, hard 12 Ethylene glycol... 360 420 Li ht 420 900 Clear. very soft i3 Diethylne glycol-.. 100 360 Ye low 30 45 ar, soft.

14 Triethylene glycol 46. 120 Light brown.... 60 85 Do, 15' Tetraethylene glycol" 40' --225 do I 120 v 900 Do. l6 Hexaethylene glycol" 40 $5. do 100 900 Do. 17 Glycerol 4 108 1,440 Clear. li old.

18 Glycol ethyl ether 21 .40 Lllht 93 120 Clear, 80 t. 19 ggggf a as. so --.--dn.... 200 400 Do. 20 Ethyl lactate- 21' 40 ....do...... 20 20 21 Ethylaoetate.. 22 41 o... 10 L l4 O que, hard. 2.3 23333:- ?t g 3 it "J 24' Cycloheian o 17 8 7 l0 Opa ue,hard. 25 Chloroiorm l7 1 36 ll 12 o, 26 Ethylene dichloride-.- 78 120 24 120 Cleansoit. 27 Ethylene dibromide... 37 v 62 a 26 120 Do. I 28 Ethylene chiorhydrin- 44 84 *45 300 Do. 29 Glyeerolmonoehlorh drin '44 280 20 500 Do. 30 Glyeeroidichlorhydr 68 345 160 300 Do. 31 Nitromethane 17 46 l0 l6 Cloudy, hard. 32 Nitroethsne 16 10 15 o. 33 iil'oplloillitrile '25 46 23 120 'I|:|rbid,ha rd.

co 0 34 fi l? 75 a 11 35 vs 110 Clear, hard.

0c 0 35 Tom, 25. as on aoo 600 Clear, soft. as gggggggg 2; er n Q no 000 Do. Alcohol, 75 {w1su1ce&,2s%. m 53 ""f 9- 38 A] grylaloh 100 Will w- 3 7 Cleanhard. co 0 Furfurylaleohol 77 40 ater 17 35 L1 14 20 O a'qne,hard. 41 None 7 35 Y W- 7 11 C ear, hard.

Nozel. I: I a M I p In the table dust free means the time required ished to a smooth surface. The finish was un- 'for the mm to set up to a non-tacky but soft condition and represents the earliest time at which the s eed of drying and recoatinz. However,

necessarily thick and was designed to illustrate during a period of four months of exposure no indication of checking was observed, although a similar finish obtained in the same way but which contained no plasticizer showed pronounced checking in a few weeks.

The following are other examples of liquid resin bases which, when a gel-stabilizer, plasticizer-and curing accelerator have been added, yield quick drying varnishes.

Example 3 Grams Urea-.. (1 mole) 60 Amylphenol "(.04 mole) 6.5

continued for 2 hours, after which water was removed under reduced pressure. The product was a clear varnish of brushing consistency.

Example 4 Grams Urea (1 mole) 60 37 aqueous formaldehyde (2.5 moles) 200 Furfuryl alcohol (1 mole) 98 Example 5 Grams Urea (1 mole) 60 Amylphenol (.12 mole) 20 37 /2% aqueous formaldehyde (2.5 moles)-.. 200' Furiuryl alcohol (l.1 moles) 110 Amylphenol, furfuryl alcohol and formaldehyde were heated to boiling under reflux and to the hot solution the urea dissolved in 30 g. of water Example 3.

' I Grams Urea (1 mole) I v 60 Amylphenol (.04 mole) ..-.e 6.5 Formaldehyde solution (2.57 n'1 o1es).. 206 Furfuryl alcohol-(1.4 moles), 144 Solution containing 0.056 g. KOH 2.5

boiling under reflux for 4/2 hour and to each oxalic acid equivalent to the alkali was added. Refiuxing was continued for 2 hours after which the solutions were dehydrated.

The product of Example 6 was cloudy and dark-colored; the film' (after adding 0.4% sulfuric acid) dried fastbut showed very poor water-resistance compared with Example 3. The product of Example 7 was light- -colored and dried rapidly to a light-colored'fllm of high waterresistance; The range of formaldehyde required in the products of this invention include from about 2 to '4 moles of formaldehyde per mole of urea. I

In the followinglexample the proportion of T furfuryl alcohol was increased over that of.

This varnish was prepared in the same manner as Example 3. When first prepared the solution was clear but clouded on standing for 48 hours. When applied as a film the solution, to which acid and alcohol were added as in the product of Example 1, dried rapidly with a pronounced yellow color. ,Also' the acidified solution showed a lower working time than Example 1.

The amount of furfuryl alcohol used in the products of the present invention should be substantially 1 mole per mole of urea (or urea+ phenol). The amount may be as high as 1.1

moles but larger amounts cause yellowing.

Lower amounts produce bases too heavy for brushing, unless thinned excessively. Furthermore, it' is impractical to thinaliquid varnish base with furfuryl alcohol to reduce the viscosity,

was added. Heating was continued for 2 hours.

The solution was filtered to remove a small amount of insoluble material (about 1 'g.) and the clear solution was dehydrated under reduced In Examples 6 and 7 the amount of formaldehyde was varied from that used in Example 3. In both cases the ingredients were heated to since the presence of excess unreacted alcohol results in slower drying, yellow films and unstable solutions.

Specific plasticizers other than that used in Example 2 (glycerol monosulfide) are'as'follows:

A. Glycerol phthalate of acid number 54, formed by heating 1 mole of phthalic anhydride with 1.1' moles glyceroL'an excess of .polyhydric alcohol beingused in order to get a product of low acid number. High acid number substances when mixed with the liquid resin base cause instability on storage.

B. Glycerol sulfide-modified diethylene glycol phthalate 'formed by heating a. mixture of 26.5 parts glycerol monosulfide, 74 parts phthalic anhydride and 26.5 parts diet'hylene glycol at 180 C. for 1 hour.

C. A reaction product obtained by heating under reflux a mixture of 37.8 parts melamine, '74 parts aqueous formaldehyde, 367 parts glycerol monosulfide and 27 parts glycol monoethyl ether for 2 hours and dehydrating.

These plasticizers were used to form coating compositions of the following general formula:

Parts Liquid resin base (Example 3) 100 Stabilizer (denatured alcohol) 25 Drier (20% solution H2504 in alcohol) 3 Plasticizer 20 These coating compositions dried to a recoatable stage in less than an hour and formed light colored films. The compositions had a working time of about 24 hours at 65 F.

The working time of the acidified compositions of this invention may be lengthened considerably by keeping them cool.

What I'claimis:

1. A coating composition comprising a solution containing a condensation product of furturyl alcohol, urea and formaldehyde in the proportions of from 2 to 4 moles of formaldehyde and substantially 1 mole of furfuryl alcohol per mole of urea, a drying accelerator therefor comprising an acid, a stabilizer comprising .a monohydric ing accelerator is an acid of dissociation greater than 1x10- and present in amount suflicient to cause rapid drying to light-colored films.

4. A coating composition comprising an acidifled solution containing a condensation product of amylphenol, urea, furfuryl alcohol and formaldehyde, an ethyl alcohol stabilizer and gly i rol monosulfide-as a plasticizer, the condensation product being formed from substantially '1 mole 25 alcohol.

5 5. Process of making acoating composition ,which dries rapidly to a light-colored fl1m,'com prising providing a solutioncontaining furiuryl alcohol-modified urea-formaldehyde condensation product formed from substantially 1 mole 10 of furiuryl alcohol and from 2 to 4 moles of 'iormaldehyde per mole of urea, a plasticizer therefor, and a stabilizing solvent comprising an aliphatic monohydric alcohol of less than 5 carbon atoms and adding from 0.3 to 0.7 per cent of an'acid thereto of dissociation constant greater than 0.01.

6. The composition of claim 1 wherein the plasticizer is a glycerol sulfide.

'7. The composition of claim 1 wherein the plasticizer is a reaction product 01 a polycarboxylic acid and a polyhydric alcohol.

8. The composition of claim 1 wherein the plasticizer is a reaction product or a glycerol sulfide, a polycarboxylic acid and a polyhydric FRANK B. ROOT. 

